JPH02103537A - Image forming method - Google Patents

Abstract

PURPOSE:To improve the sharpness of printing areas by assigning the halogen compsn. of silver halide emulsions in processing of a negative type photosensitive material having a specific hydrazine deriv. by a developing soln. CONSTITUTION:The negative type photosensitive material contg. the hydrazine deriv. of the formula I in the emulsion layers or other hydrophilic colloidal layers, is processed by the developing soln. of <=pH 11.2 to form the hard- contrast B/W images of >=G8. The silver halide particles are formed of octahedron or fourteenfaced parhiles at this time. In the formula I, R1 denotes an aliphat. group, arom. group; R2 denotes a hydrogen atom, alkyl group, etc.; G1 denotes a carbonyl group, sulfonyl group, etc.; A1, A2 denote a hydrogen atom or one thereof denotes an alkyl sulfonyl group, aryl sulfonyl group or acyl group. The reproducibility of the printing images and dots are improved in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention is directed to silver halide photographic material f4 (particularly negative type).

(Prior Art) It is known that certain silver halides can be used to form extremely high contrast photographic images, and methods for forming such photographic images are used in the field of photolithography.

Conventionally, a special developer called a Lith developer has been used for this purpose. Liss developer contains only hydroquinone as a developing agent, and uses sulfite as a preservative in the form of an adduct with formaldehyde so as not to inhibit its infectious development properties, and the concentration of free sulfite ions is extremely low. (iffi usually 0°1 mol/l or less).

Therefore, the Lith developer has a serious drawback in that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days.

U.S. Pat. No. 4,224,401 and U.S. Pat.
, No. 168,977, No. 4.166.742, No. 4,311,781, No. 4.272.606, No. 4. 211. No. 857, same No. 4,243.739
There is a method using a hydrazine derivative described in No. 1, etc. According to this method, photographic properties with ultra-high contrast and high sensitivity can be obtained, and since it is permissible to add a high concentration of sulfite to the developer, the stability of the developer against air oxidation is better than that of the lithium developer. A dramatic improvement in comparison.

However, ultra-high contrast image forming methods using these hydrazine compounds strongly promote contagious development, so when photographing character manuscripts with low contrast (especially fine lines in Mincho fonts), areas that should be thin white backgrounds are used. It turned black until
There was a problem with the text becoming black and unreadable. Therefore, if the exposure was reduced to match the thin lines of the Mincho typeface, the problem was that the exposure latitude was narrow, conversely making the Gothic characters look worse. A similar problem also occurs in halftone image photography, which has disadvantages in image quality such that even the parts of the knitting dots that appear as a white background are easily blackened and the halftone gradation becomes very short.

The cause of this is that the contagious development property of high-contrast development using hydrazine compounds is strong, and the low-exposed or unexposed areas adjacent to the exposed areas are developed.To prevent this, contagious development is There has been a desire to develop a method for suppressing image enlargement due to the image area, and a method for producing a development effect that suppresses development of areas adjacent to an image area (hereinafter referred to as micro-development suppression).

A good way to suppress infectious development is to reduce the amount of nucleating agent added or to lower the pH of the developer, but this will result in softer gradations and loss of image sharpness. , there are practical problems. Furthermore, various attempts have been made to provide microscopic development inhibition in the nucleating development system, but no satisfactory method has yet been found.

In the present invention, nucleation development is controlled by controlling the pH of the developer to be 11.2 or less, that is, image enlargement and micro ff1l control. Normally, if pII is set to 11.2 or less, high contrast at C8 or higher will not occur, but
As described in No. 2-15788, sufficient high contrast can be achieved by using a nucleation accelerator in combination.

In addition, development at a pH of 11.2 or lower has weaker contagious developability and smaller image enlargement than high-contrast development at a higher pH, and development of unexposed or low-exposed areas adjacent to the image area is difficult. It was found that the microscopic suppression was remarkable. Further analysis revealed that this development effect is closely related to the crystal habit of silver halide.

On the other hand, with pHIL of 2 or higher, it was easy to obtain ultra-high contrast images of C8 or higher, but the stability of the developer was poor, the developing agent was oxidized and deteriorated, and CO in the air was absorbed. Photographic properties often change due to pH fluctuations. Further, there is almost no developing effect as seen at p II of 11°2 or less, and the light/gold exposure latitude is narrow, so improvements have been desired.

(Objective of the Invention) The first object of the present invention is to improve the reproducibility of lines and halftone dots (
An object of the present invention is to provide a silver halide photographic window optical material (having a wide exposure latitude).

The second object is to provide a method for forming ultra-high contrast images in a system using hydrazine, in which performance can be stably maintained using a stable developer.

(Disclosure of the Invention) The above object of the present invention is to have at least one silver halide emulsion layer on a support, and to have a hydrazine derivative of general formula (I) in the emulsion layer or other hydrophilic colloid layer. A method of processing a negative photosensitive material with a developer having a pH of 11.2 or less to form a high contrast/W image of 0.8 or higher, characterized in that the silver halide grains are octahedral or tetradecahedral grains. This was achieved using an image forming method.

General 2N) In the formula, Rt represents an aliphatic group or an aromatic group, and Rt
is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group,
It represents an aryloxy group, an amino group, a carbamoyl group, or an oxycarnebonyl group, and G is a carbonyl group, a sulfonyl group, a sulfoxy group, or an atom.

Both A's are hydrogen atoms, one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted acyl group.

-C In formula (1), the aliphatic group represented by Rt preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
20 straight, branched or cyclic alkyl groups. The branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms, and the alkyl group may be an aryl group,
It may have a substituted tA group such as an alkoxy group, a sulfoxy group, a sulfonamide group, or a carbonamide group.

- The aromatic group represented by R1 in the bracket ([) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.

Here, the unsaturated heterocyclic group may be combined with a monocyclic or bicyclic aryl group to form a heteroaryl group.

For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring,
Examples include isoquinoline ring, benzimidazole ring, thiazole ring, and benzothiazole ring, among which those containing a benzene ring are preferred.

Particularly preferred as R1 is an aryl group.

The aryl group or unsaturated heterocyclic group of R7 may be substituted, and typical substituents include a linear, branched or cyclic alkyl group (preferably one having 1 to 20 carbon atoms), an aralkyl group (preferably a monocyclic or bicyclic alkyl group having 1 to 3 carbon atoms), an alkoxy group (preferably a carbon number of 1 to 20), a substituted amino group (preferably an alkyl group having 1 to 20 carbon atoms) an acylamino group (preferably one having 2 to 3 carbon atoms), a sulfonamide group (preferably one having 1 to 30 carbon atoms)
), ureido group (preferably 1 to 30 carbon atoms)
) etc.

-S The alkyl group represented by R1 in formula (1) is preferably an alkyl group having 1 to 4 carbon atoms,
It may have a substituent such as a halogen atom, cyano group, carboxy group, sulfo group, alkoxy group, or phenyl group.

The aryl group represented by R8 is preferably a monocyclic or bicyclic aryl group, and includes, for example, a benzene ring. This aryl group may be substituted with, for example, a halogen atom, an alkyl group, a cyano group, a carboxyl group, a sulfo group, or the like.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

The acyloxy group is preferably a monocyclic one, and the substituent includes a halogen atom and the like.

The amino group includes an unsubstituted amino group and a carbon number of 1 to 10.
Preferred are alkylamino groups and arylamino groups, which may be substituted with alkyl groups, halogen atoms, cyano groups, nitro groups, carboxy groups, etc. Carbamoyl groups include unsubstituted carbamoyl groups and those having 1 to 10 carbon atoms. An alkylcarbamoyl group and an arylcarbamoyl group are preferred, and may be substituted with an alkyl group, a halogen atom, a cyano group, a carboxy group, or the like.

The oxycarbonyl group is preferably an alkoxycarbonyl group or an aryloxycarbonyl group having 1 to 10 carbon atoms, and may be IIA-grouped with an alkyl group, a halogen atom, a cyano group, a nitro group, or the like.

Among the groups represented by R2, preferred is G.

is a carbonyl group, a hydrogen atom, an alkyl group (e.g., methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, etc.), an aralkyl group (e.g., 0-hydroxybenzyl group) etc.), aryl groups (e.g. phenyl group, 3.5-
(dichlorophenyl group, 0-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, etc.), and a hydrogen atom is particularly preferred.

Furthermore, when G is a sulfonyl group, R. is an alkyl group (e.g. methyl group), an aralkyl group (e.g. O
-hydroxyphenylmethyl group), aryl group (e.g. phenyl group etc.) or substituted amino S (e.g.
dimethylamino group, etc.) are preferred.

When G1 is a sulfoxy group, R is preferably a cyanobenzyl group or a methylthiobenzyl group, and ○ is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group, or a phenyl group, with a phenoxy group being particularly preferred.

When Gl is N-substituted or unsubstituted imino methylene,
Preferred R2 is a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group.

As a substituent for Rt, R. In addition to the substituents listed above, for example, acyl groups, acyloxy groups, alkyl or aryloxycarbonyl groups, alkenyl groups, alkynyl groups and nitro groups can also be applied.

G in formula (1) is most preferably a carbonyl group.

Moreover, R2 is G, -R. split the part from the residual molecule, −
It may be one that causes a cyclization reaction to produce a cyclic structure containing an atom of the G-R□ moiety, and specifically, one that can be represented by the general formula (al).

General formula fa) Rs-Z In the formula, Zl nucleophilically attacks G, and G.

R s Z is a group that can split one moiety from the remaining molecules, R3 is one hydrogen atom gap from R□, and 2.
makes a nucleophilic attack on G. , R, , Z, can generate a cyclic structure.

More specifically, Zl easily undergoes a nucleophilic reaction with 61 when the hydrazine compound of general formula (I) generates the following reaction intermediate by oxidation etc. to form R1 N==N Gl-Rt ZlR, -N- N
A group that can split a group from G1, specifically 0!1
, SH or NHR= CRs is a hydrogen atom, an alkyl group, an aryl group, -COR, or -So. RS, where Rs represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc.) It may be a functional group that directly reacts with 61, such as COOR (where 011, SH
, N.H.R.

- C--R. -C-R. (R., R, represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group) by reacting with a nucleophile such as a hydroxide ion or a sulfite ion.6. It may also be a functional group that is capable of reacting with.

In addition, the ring formed by G1, Rs, and Z+ is 5
Among those represented by general formula (a), preferred are those represented by general formulas (b) and (C).

General De((b) In the formula, Rh"=Rh' is a hydrogen atom, an alkyl group (preferably one having 1 to 12 carbon atoms), an alkenyl group (preferably one having 2 to 12 carbon atoms), an aryl group (preferably one having 2 to 12 carbon atoms) B is an atom necessary to complete the 5R ring or 6R ring which may have an ili group, and m, n is O or 1, and (n+m) is 1 or 2.

Examples of the 5R or June ring formed by B include a cyclohexene ring, a cycloheptene ring, a nzene ring, a naphculene ring, a pyridine ring, and a quinoli ring.

Zl has the same meaning as in general formula (a).

-Rc (-N+-T-(-CRcI Rc''-)-r-2゜In the formula, Rc' and R% are hydrogen atoms, alkyl groups, alkenyl groups, aryl groups, halogen atoms, etc.) and may be the same or different.

Rc3 represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

p represents 0 or l, and 9 represents 1-4.

Re-1Re'' and Rc may be bonded to each other to form a ring as long as the structure allows Zl to make an intramolecular nucleophilic attack on G.

Rc'sRc'' is preferably a hydrogen atom, a halogen atom,
or an alkyl group, and R% is preferably an alkyl group or an aryl group.

9 preferably represents 1 to 3; when 9 is 1, p represents 1 or 2; when 9 is 2, p represents 0 or l; when 9 is 3, p represents 0 or l, and when q is 2 or CR when 3
c'Rc' may be the same or different.

Zl has the same meaning as in general formula (a).

At, At represents a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms, and an arylsulfonyl group (preferably a phenylsulfonyl group or a Hammett substituent constant having a sum of −0
, a phenylsulfonyl group substituted so as to have 5 or more), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a sum of Hammett's i constants of -0,
A benzoyl group that has been ItA-treated with an ItA of 5 or more, or a linear, branched, or cyclic unsubstituted or substituted aliphatic acyl group (substituents include, for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group) , carboxy group, and sulfonic acid group.)) A, , A
, is most preferably a hydrogen atom.

R1 or Rt of the -Iu formula (1) may incorporate Ballast 7J, which is commonly used in immobile photographic additives such as couplers.

The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy W,
You can choose from alkyl phenoxo-kyo, etc.

-C R1 or R1 in formula (1) may have a group incorporated therein that enhances adsorption to the silver halide grain surface. Examples of such adsorption groups include a thiourea group, a heterocyclic thioamide group, and a mercaptohetero U.S. Pat. No. 4,385.108, U.S. Pat. No. 4,459, for ring groups, triazole groups, etc.
, No. 347, JP-A No. 59-195, 233, No. 59-
200゜231, 59-201,045, 59
No. 201.0.16, No. 59-201,047, No. 5
9-201,048, 59-201,049, JP-A-61-170.733, JP-A-61-270,744
No. 62-948, patent application No. 62-67.508,
Examples include the groups described in No. 62-67.501 and No. 62-67.510.

-C Specific examples of the compound represented by formula (1) are shown below.
However, the present invention is not limited to the following compounds.

l-3) ■-5) I-6) l-8) CIIxCHiCII□5H Sl+ Sl+ ■! -26) I -44) In addition to the above-mentioned hydrazine derivatives, RESEARCHDISCLO5LIRE
Item23516 (November 1983 issue, P, 3
46) and the documents cited therein, as well as U.S. Pat.
No. 76.364, No. 4,278,748, No. 4.38
No. 5,108, No. 4,459,347, No. 4,560
, No. 638, No. 4,478,928, British Patent No. 2,0
11,391B, JP-A-60-179734, JP-A-61-170.733, JP-A-61-270.744,
No. 62-948, EP No. 217.310, Patent Application No. 1983
-175.234, 61-251,482, 6
1-268.249, 61-276.283, 62-67.508, 62-67゜529, 6
2-67.510, 62-58.513, 62
-130.819, 62-143,469, 6
2-166.117 can be used.

The amount of the hydrazine derivative added in the present invention is 1X10-h mole to 5X10 mole per mole of silver halide.
-2 mol is preferable, and a particularly preferable addition amount is in the range of 1X10-' mol to 2X10-'' mol.What is the best way to obtain a high-contrast image of C8 or higher with a developer having a pH of 11.2 or less? Although any method may be used, a compound of general formula (n) can be used as a nucleation accelerator.

- Monna (11) (In the formula, Y represents a group that adsorbs to silver halide. The group will be υ.211i]i
Expressed as a linking group. A is a monovalent linking group. B represents an amino group, an ammonium group, or a heterocyclic ring, and may be substituted with an amino group Vi. m represents /, 2 or 3, and n represents O or /. ) The group in which Y adsorbs to Tenwacho halogen/silveride can be derived from a fluorine-containing heterocyclic compound.

When Y is an atom-containing cyclic compound, the general formula (II) is used.
The compound is coated with the following pattern ([I).

- Monana (III) In the formula, lll-10-1fc is /f5, m is /9.
2 ma 9#-iJ 金聚わし, n is Omano is l 金聚wa ding.

-fl-(X←A-B)m has the same meaning as that in -Momonena (1) above, and Q is a carbon atom,! A group of atoms necessary to form a J or t negative heterocycle consisting of at least one type of elementary atom, oxygen atom, or sulfur atom is selected. Further, this 'a', the elementary ring, may be fused with a carbon aromatic ring or a diagonal aromatic ring.

As the heterocycle formed by Q, for example, each tN
Substituted or unsubstituted indazoles, benzimidazoles, benzotriazoles, benzoxazoles,
Ins thiazole fabric, imidazole head, thiazole fabric,
Oxazoles, triazoles, tetrazoles, azaindenes, pyrazoles, indoles, triazines, pyrimidines, birins, quinolines, etc. are included.

M is a hydrogen atom, an alkali metal atom (e.g., a sodium atom, a potassium atom, etc.), an ammonium group (e.g., a trimethylammonium group, a dimethylbenzylammonium group, etc.), or an alkali metal when PVl=H under an alkali condition. Groups that can become atoms (for example, acetyl, cyanethyl, methanesulfonylethyl, etc.) are excluded.

In addition, these V-rings include nitro atoms, halogen atoms (e.g., 1 violet atom, A-group atoms, etc.), mercapto atoms, cyano groups, and substituted or unsubstituted alkaline atoms (e.g., methyl, ethyl, etc.). Group, propyl a!:, l-7'thyl, 77 noethyl 11 methoxyethyl, methoxyethyl i, number L aryl:; , 4'-dichlorophenyl, naphthyl, E, etc.), alkenyl (but),
Aralkyl group (5'II /-t”i
, ≠-Methyl benzyl, fuetyl, etc.), alcoquinone (e.g., methokino, etho?7 groups, etc.),
Aryloxy (e.g. fenoki / 茫, μmm metsonofenoki 7 group), aryloxy (ill eshbomethylthio, ethyl thear,, t;, metode/ethyl thean), arylthia yun (dlj: i” Phenylthia, S), sulfonyl (, comethanesulfonyl, ethanosulfonyl f, p-) luenesulfonyl, 4), carbamoyl (yll, ↓I, carbamoyl), methylcarbamoyl, phenyl Carbamoyl, 4), sulfamoyl (Le Z, C%I, %ffi, sulfamoyl, methylsulfamoyl, phenylsulfamoyl 3, etc.), carbonamide can (1F!I, acetamido group, inzamide group, etc.), sulfonamide group (for example, methanesulfonamide group, penze/sulfonamide group, p-toluenesulfo/amide T, 4), aralkyl group (e.g. acetyl quinone, benzoyl X, 4), sulfonyl group Open group (f'4i: gomethanesulfonyloxysake, →).

Ureido group (IZIJ is an unsubstituted ureido group, methylfreido group, ethylureido group, funinylureido group,
etc.), Thioureido 3 (Henjiebini, Oh's Thioureido, Meterte/Rureido Tsuki, etc.), A/R So (1
Evening 1j (zuacetermo, benniyi/I-ki, 碍),
Hete C burial (Arrangement: ba/-mo, thorinomo, l-piperidino, -1-biridyl poison, hiro-biridyl group, !-thienyl, /-pyrazolyl, l-imidanlyl, coachtrahydrofuryl) So, Te:・Rahydrochenilmo, 4)
, Otishical〆niru'ES (1 row jba metokino sword
Zenil Ju, Fenoki/Carbonyl Jo, etc.), Oxy Katana Luponylaminosa (eg Hametoki/Katana Rubinylamino 7,
fenoki/sword rubinylamino, -one ethyl heinruochi 7 power ruhinylamino, etc.), amine groups (e.g., methoxyamino, dimethylamino, methoxyethylamino, anilino, etc.), carbonpomata i That fence, suru:'r, :/43 Mano may have 1 god with that salt, hydroquine, etc. --N- and 1 and the like are directly between Q and Q, and are directly separated from each other by pJ4. may be bonded via a methyl ethylene group, /-methylethylene group, number)'. Hydrogen atoms, each with a false or unsubstituted alkyl group (e.g. methyl 1, ethyl group, propyl group, n-
Butyl (Yu, present), one radical or rt-free exchangeable aryl group (
For example, phenyl, comethylphenyl, =), a=
Or alkenyl jin (propenyl jin, / - methylvinyl king, title) in the form of alkenyl jin (propenyl jin, /-methylvinyl king), Manzuki is violet chivalry or a yan lie ``aral'' in ru 6 (for example, (・1 benzyl , 4).

Ar11 has a valent base, and as a λ-valent O link, W5A-=fc is a fractional alkylene group (ψ1j is methylene, ethylene group, propylene group, ethylene group, hekylene i, /-). ``Chile ethyle'' 5.4), K's name is a separated alkenylene group (for example, vinylene ff, /-methyl vinylene, etc.), a straight chain is separated into ``fc'', a 7-alkylene group (yiJ, etc.) Examples include phenylene, naphthylene, etc.), arylene (i41ifd phenylene, naphthylene, etc.), etc.The above X and A, which can be expressed as thorn V in humans, are further replaced with Tt by the width of pressure -f. MoyoX/).

B's t I also think that Amine 3, which is a substitute for agitation, is a one-part formula Il +), which makes it very cheap.

- Throwing formula (Vllll) (In the formula, approximately 11 FL12 may be 1 town - or different, each hydrogen atom, ・Shagoro or unsubstituted carbon number/~30 alkyl, alkenyl ji 17tFi represents an aralkyl group, these groups are linear (e.g. methyl group,
ethyl group, n-propyl group, n-butyl group, n-octyl group, allyl group, 3-butenyl group, benzyl group, /-naphthylmethyl group, etc.), separation (e.g. isopropyl group, t-octyl group) , etc.), or may be cyclic (eg, cyclohexyl group, etc.).

Also, the box 11 and the box 12 may be connected to form a metal filling,
One of them, t7t, may be cyclized to form a saturated heterocycle containing more than one heteroatom (e.g., oxygen atom, sulfur atom, divalent atom, etc.), such as a pyrrolidyl group. , piperidyl group, morpholino group and the like. Examples of substituents for R11, R, and 12 include carxyl group, sulfo group, cyano group, halogen atom (e.g., fluorine atom, salt compound, and bromine atom), hydroxyl group, and carbon number. Alkoxycarbonyl groups having λO or less (e.g., methoxycarbonyl group, ethoxyruzenyl group, phenoxoruzenyl group, benzyloxycarbonyl group, etc.), alkoxy groups having 20 or less carbon atoms (
For example, methoxy group, ethoxy group, benzyloxy group, phenethyloxy group), monocyclic 7 with carbon number -〇 or less
lyloxy group (e.g., phenoxy group, p-tolyloxy group, etc.), acyloxy group having 20 or less carbon atoms (e.g., acetyloxy group, propionyloxy group, etc.), acyl group having 20 or less carbon atoms (e.g., acetyl group 1. propionyl group, benzoyl group) group, metal group, etc.), carbamoyl group (e.g. carbamoyl i, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, pyridinocarbonyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group) , morpholinosulfonyl group, piveridinosulfonyl group, etc.), carbon da
o or less acylamino group (for example, acetylamino group, propionylamino group, benzoylamino group, mesylamino group, etc.), sulfonamide group (ethylsulfonamide group, p-)luenesulfonamide group, etc.), carbon number 2.
0 or less carbon amide group (e.g. methyl carbon amide group, phenyl carbo/amide group, etc.), carbon HE120
Examples include the following ureido groups (for example, methylureido group, phenylureido group, etc.), amino groups (synonymous with -tsusuriyo (Vllll)), and the like.

The ammonium group of B is represented by the general formula (1x).

(Zo).

(In the formula, R13, B14 R15 is the general formula (V
lll) i'c oker R"
group, and Ze represents an anion, such as a no-ride ion (e.g., αe, Bre, Iθ, etc.), a sulfonate ion (e.g., trifluoromethanesulfonate, paratoluenesulfonate, benzenesulfonate-F), and Ze represents an anion.
, /R5-benzene sulfonate, etc.), sulfato ions (eg, ethyl sulfate, methyl sulfate, etc.), per/p lard, tetrafluoroborate, and the like. pF'i0 is represented by /'i, and is O when the compound forms an inner salt. ) The diatomic heterocycle of B contained at least one or more diatomic atoms! Further, it is a #iz membered ring, and these rings may have a substituent or may be fused with another ring. Examples of the diatomic heterocycle include imidazolyl group, pyridyl group, and thiazolyl group.

Among the general formulas (I[), preferred are the following -f
f' formula (IV), (V), tV+) -tfcu
(Vll) -c compounds are mentioned.

General formula (1) General formula ( General formula (vl) (X-)-A-B General formula (Vll) (In the formula, +x+-A-B.

mH has the same meaning as that of - Tsuzuriyo (IL). zl, z2 and Z3 are the above-mentioned % formula % definition, or...rogen atom, alkoxy group with carbon number of 0 or less (e.g. methoxy group), hydroxyl, hydroxyamino group, substituted and unsubstituted The substituents can be selected from the above-mentioned R'', R''2.ot substituents.

However, at least one of 2□, z2 and Z3 is +X→
It is synonymous with -A-B.

Further, these heterocycles may be substituted with substituents applicable to the heterocycle of general formula (IL).

Examples of compounds represented by general formula (1) are shown next, but the present invention is not limited thereto.

■-/.

And-Yu I[-3 ■-Hiroshi ■-yo the law of nature ■-t α h ■-y.

■-/.

"-72 II-/J.

■-/a (CH2+2NH2 ■-7r ■-/l.

■-/r.

■-2 Pressure: 23° ■-ko2 ■-22 ■-xr.

■-3/ II-J ■-,y5! ■-t, t.

■-≠7 t4t2 ■-g3゜ll-4=μ ■-u j 'fl-t, tt α Gesellschaft (Be
Richte der L)eutschen
Chemischen Ge5ellschaft
)2 r, 77 (/frij), JP-A-210-=3'7
4LJt issue, same! /-jλ31, US Patent J, 2P1
．． 7 to 1 U.S. Patent No. 3,376.310, Berichte
Der Deutschie/l Hemifusien Gesellschaft (B
erichte der L)eutschen Ch.
emischen Gesellschaft) s,
2,! AI(/119>, same ta, it, tri(ir
yt), Journal of Chemical Science and Technology (
J, Chem, Soc.

/riJj, /rOt, Journal of the American Chemical Society (J, Am.

Chem, Sac, ) 7t, 4t000 (/P412)
, US Patent 2. zr! 1Jrr issue, same x, rai
.

Octopus μ, Advances in Heterocyclic Chemistry (Advanceo 1nHeter)
cyclic chemistry）ヱ、／ふ! (
/Pbuj), Organic Synthesis (Organi
c 5ynthesis) ■,lli(/riZ3
), Journal of the American Chemical Society (J, λm, Chem, Soc,)4tj,
23ri0 (/9λ3), Hemisie Sho Berichte (Chem
ische Beric'hte)ri, 4ttt(/
r7j), 9 Kosho t, to-sra riwo issue, Japanese Patent Application Publication No. 1973
-1903≠, US patent! , IO&, 4't7, same 3. Da 0. No. t70, 2, 27/.

, 2.2 issue, same! , /37. ! No. 71, 3.74t
r, ott issue, same J, j//, ttJ issue, same 3゜oto
, oa; No. 1, same! , 27/, /j No. 41, same 3, +2
31. A9 No., same J, Jft,! No. 29, same J, /μ
r, ott No., Special Publication No. 4L3-μ/-31, U.S. Patent No. 3. tiB≦/j issue, same 3.4! -〇, ≦4'J No., same J, 071, Hirotj No., same.

1st, tos, same, 11. tOt issue, same 2,! fu
'l, No. 407, same, 2. Rijj, DaOda issue *Opened in 1987
-20 pieces! 3/ issue, 17-/17, 0.23 issue, 17-/bu μ, 73j issue, same issue o-to.

t3ri, zr-iti, λ3J, j7-/g,
J' j J issue, same! ter iti, z≠, same otsu O-
/3073/ issue, same t O-/ J f, j 4Lt issue, same! r-x3. rs2, same jt! -/! ri, 122
No. 39-/! ri, / j J issue, same tO-, 2/7
,3! No. r, same &/-40. Ko JJ' issue, special public Sho to-
λri, 3ri No. 0, AO-2ri, 3ri No. 7, 60-/
3! , OA No. 7, OA 7/-/, 4' J No. 7, etc.

The optimum amount of these accelerators to be added varies depending on the type of compound, but it is desirable to use them in the range of 1.0 x 10-3 to 0.5 g/rr, preferably 5.0 x 10-' to 0.4 g/rr+. These accelerators can be used in a suitable t-vehicle (HIO,
It is dissolved in alcohols such as methanol and ethanol, acetone, dimethylformamide, methylcellosolve, etc.) and added to the coating solution.

A plurality of types of these additives may be used in combination.

The silver halide used in the present invention is, for example, T,
II, “The Theory of
thePhotographic Process
'4th edition, published by Macmiilan, 977) 88~
It is produced by methods such as the neutral method, acidic method, ammonia method, forward mixing, back mixing, double jet method, Chondral double jet method, core shell method, etc. described in the literature such as page 104.

If necessary, grain size, grain shape, distribution, etc. can be controlled by using silver halide solvents such as thioethers and thioureas.

There are no particular limitations on the grain size, grain size distribution, crystal habit, morphology (normal crystal, twin crystal, etc.) of the silver halide grains, but silver halide grains with a relatively uniform grain size of 0.05 to 0.8 μm are preferred.

The particle size distribution is preferably monodisperse; monodisperse means a dispersed system in which 95% of the particles fall within ±60%, preferably within ±40% of the number average particle size. It is preferable to have one.

The halogen composition includes silver bromide, silver iodobromide, silver chlorobromide,
Silver chloroiodobromide is preferred, and the bromine content must be 70 mol% or more.

Preferably B "80 mol% or more, especially 13r 90 mol%
The above is preferable. The silver iodide content is usually 10 mol% or less, preferably 5 mol% or less.

In the silver halide emulsion used in the present invention, cadmium salt, sulfite, lead salt, thallium salt, rhodium salt or its complex salt, iridium salt or its complex salt, etc. are allowed to coexist in the silver halide grain formation or physical ripening process. Good too.

In particular, iridium salts range from 10-I' to 10-s mol/A
g1 mol, and rhodium salt is 104 to 10-4 mol/Δg
Preferably, 1 mol is added.

These silver halides may be chemically sensitized after forming grains and undergoing a desalting step, or may be used without chemical sensitization. Examples of chemical sensitizers include sulfur sensitizers such as sodium thiosulfate and thiourea; noble metal sensitizers such as gold sensitizers, specifically chlorauric acid salts, gold trichloride, etc., and palladium sensitizers such as palladium sensitizers. Palladium chloride, palladate chloride, etc., platinum compounds, iridium compounds, etc.: Selenium sensitizers, such as selenite, selenourea, etc.: Reduction sensitizers, such as stannous chloride, polyamines such as diethylenetriamine, sulfites. , can be chemically enhanced by chemical sensitizers such as silver nitrate or in combination.

The enhancing dyes used in the present invention include various sensitizing dyes known in the field of photographic window light materials, such as cyanine dyes, merocyanine dyes, complex cyanine dyes, complex melonanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemicyanine dyes. Included are oxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. For these dyes, any of the basic heterocyclic nuclei commonly used for cyanine dyes can be used. Namely, viroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus,
Oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; , indolenine nucleus, benzindolenine I, indole JL benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, penzimiguzole nucleus, quinoline maki, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, 1 thiazolidine-2,4-dione,
Rhodanine cores, thionoyl bituric acid solutions, and other May-June heterocycles can be applied.

Useful sensitizing dyes include, for example, German Patent No. 929,080;
U.S. Patent No. 2,231,658, 2°493.748
No. 2,503,776, No. 2 519.001, No. 2,912.329, No. 3,656,959,
No. 3,672,897, No. 3,694,217, British Patent I, No. 242.588, Japanese Patent Publication No. 14030-1973
No. 53-137] No. 33, JP-A-55 = 450
15, as described in Japanese Patent Application No. 61-79533.

These enhancing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

Useful enhancing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are listed in Research Disclosure+ in addition to the above.
176S17643 (issued December 1978) No. 23
It is described in sections A-J on page 2.

Here, the aggravating dye or the like can be added to any step of the photographic emulsion manufacturing process, or can be added at any stage after the emulsion is manufactured and immediately before coating.

Examples of the former include particle formation, physical ripening, and chemical ripening.

The aggravating pigment used in the present invention can be mixed in an aqueous solution or water.
A miscible NTG agent is added to the silver halide emulsion as a solution dissolved in methanol, ethanol, propyl alcohol, methyl cellosol, pyridine, etc.

The timing of adding the sensitizing dye used in the present invention to the emulsion is as follows:
Preferably, the process is carried out before the emulsion is coated on a suitable support, but it may also be carried out in a chemical ripening step or in a silver halide grain formation step.

In the present invention, the preferable addition amount of the sensitizing dye is jl 1
It is appropriate to add 10-h to 10-1 mol per mole, preferably 10-4 to 10-f mol.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used especially for the purpose of supersensitization.

The light-sensitive material used in the present invention contains dyes for use as filter dyes, irradiation prevention, and other purposes.
Such dyes, which may contain water-soluble dyes, include oxonol dyes, benzylidene dyes, merocyanine dyes, cyanine dyes and Ab T4 dyes. Among them, oxonol dyes, hemioxonol dyes and benzylidene dyes are used. Specific examples of dyes that can be used are given in British Patent 5.
No. 84.609, No. 1,177.429, Japanese Unexamined Patent Publication No. 1977
-85130, 49-99620, 49-11
No. 4420, No. 52-20822, No. 59-15443
9, No. 59-208548, U.S. Patent No. 2,274,78
No. 2, same 2. 533. No. 472, 2.956, 8
No. 79, No. 3.148187, No. 3,177.078
No. 3,247.127, No. 3,540,887, No. 3575.704, No. 3,653,905,
It is described in No. 3,718,427.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazole, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles. , etc.; mercaptobiwamidine neck; mercaptotriazine cheek; thioketo compounds, such as oxiduzolinthion; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxyEl derivatives (1,3, 3a,
7) Tetrazaindenes), pentaazaindene, etc.; benzenethiosulfonic acid, benzenesulfinic acid,
Many compounds known as antifoggants or stabilizers can be added, such as benzenesulfonic acid amides, hydroquinone derivatives, and the like. Among these things,
Preferred are benzotriazoles (e.g. 5-methyl-benzotriazole) and nitroindazoles tW
(eg, 5-nitroindazole), hydroquinone derivatives (eg, hydroquinone, methylhydroquinone), and these compounds may be included in the treatment liquid.

The photographic material r1 of the present invention may contain an inorganic or organic hardening agent in the photographic milk 7F'1 layer and other hydrophilic colloid layers. For example, an active vinyl compound (1,3°5-triacryloyl- Hexahydro-8-toIJ azine, 1.3
-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-8
-triazine, etc.), mucohalogen acids, etc. can be used alone or in combination. Among them, JP-A No. 53-41221, No. 53-57257, No. 59-16
2546, 60-80846 and the active halides described in U.S. Pat. No. 3,325,287 are preferred.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention includes coating aids, 4tF antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (if successful, development acceleration, Various surfactants may be included for various purposes such as hardening, sensitization, etc.

In particular, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more and described in Japanese Patent Publication No. 5B-9412.

When used as an antistatic agent, fluorine-containing surfactants (eg, US Pat. No. 4,201,586, JP-A-60-80849) are particularly preferred.

The light-sensitive material used in the present invention may contain a water-soluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability or the like. For example, a polymer containing as a monomer component alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, etc. alone or in combination, or a combination of these and acrylic acid, methacrylic acid, etc. may be used. Can be done.

The photographic light-sensitive material of the present invention contains hydroquinone derivatives (so-called DIR-
hydroquinone).

The photosensitive material used in the present invention includes, for the purpose of promoting development,
It may contain quaternary onium salts or amine compounds described in Japanese Patent Application No. 124830/1983.

It is preferable that the silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention contain a compound having an acid group. Examples of the compound having an acid group include organic acids such as salicylic acid, acetic acid, and ascorbic acid, and acrylic acid. Mention may be made of acids, polymers or copolymers having as repeat units acid monomers such as maleic acid, phthalic acid. Regarding these compounds, Japanese Patent Application No. 60-56179 and No. 60-
No. 68873, No. 60-163856, and No. 60-
You can refer to the description in the specification of No. 195655. Among these compounds, particularly preferred is ascorbic acid as a low molecular compound, and two or more of an acid monomer such as acrylic acid and divinylbenzene as a high molecular compound.

It is a water-dispersible latex of a copolymer composed of monomer monomers having unsaturated groups.

Binders or protective colloids used in photosensitive materials include:
It is advantageous to use gelatin, but other hydrophilic synthetic polymers can also be used. As the gelatin, lime-treated gelatin, acid-treated gelatin, derivative gelatin, etc. can also be used. Specifically, research
Disclosure (RESEARCII 0ISCL)
O5LIRE) Volume 176, Ntl17643 (19
(December 1978) (7) Section IX.

In addition to the silver halide emulsion layer, the photosensitive material used in the present invention can be provided with hydrophilic colloid layers such as a surface protective layer, an intermediate layer, a filter layer, and an antihalation layer.

In addition, the photosensitive material used in the present invention has front and back distinguishability,
Back side I for the purpose of curling characteristics, halation prevention, etc.
5 (hereinafter referred to as back layer) 0 The back layer used in the present invention preferably contains a matting agent having a relatively large average particle size, particularly from the viewpoint of adhesion resistance. Particle size is 1.0μmm-1
Ou, particularly preferably 2.0 μm to 5.0 μm.

The surface protective layer also contains a homopolymer of polymethyl methacrylate, a copolymer of methyl methacrylate and methacrylic acid, magnesium oxide as a matting agent, and U.S. Pat.
Silicone compound described in No. 8, Japanese Patent Publication No. 56-2313
In addition to the colloidal silica described in No. 9, paraffin wax, higher fatty acid esters, denso, etc. can be used.

Further, polyols such as trimethylolpropane, pencundiol, butanediol, ethylene glycol, and glycerin can be used as plasticizers in the hydrophilic colloid layer.

In order to obtain photographic characteristics of ultra-high contrast and high sensitivity using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or a highly alkaline developer with a pH close to 13 as described in U.S. Pat. No. 2,419,975. It is not necessary to use a stable developer, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains 0.15 mol/E or more of sulfite ion as a preservative, and p
H9,5 to 12.0, especially when it contains a - binding margin (+) compound, p+ (11,0 to 12.0 developer)
When using a combination of general 2N) and (It) compounds, p
By using a developer of H9.5 to H12.0, photographic characteristics of sufficiently high contrast and high sensitivity can be obtained.

There is no particular restriction on the developing agent used in the developer used in the present invention, but it is preferable that it contains dihydroxybenzenes since it is easy to obtain good halftone quality, and furthermore, it is preferable to contain dihydroxybenzenes in terms of developing ability. - A combination of phenyl-3-virapritones or dihydroxybenzenes and p-
Combinations of aminophenols are preferred.

Dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, isopropylhydroquinone, methylhydroquinone, etc.
Hydroquinone is particularly preferred.

As the developing agent for l-phenyl-3-pyrazolidone or its derivative used in the present invention, 1-phenyl-3-virapritone, 1-phenyl-4,4-dimethyl-3-virapritone, 1-phenyl-4methyl-4- Examples include hydroxymethyl-3-pyrazolidone.

Examples of the p-aminophenol developing agent used in the present invention include N-methyl-P-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, and N-(4-hydroquinphenyl). Examples include glycine, among which N-methyl-p-aminophenol is preferred.

The amount of developing agent is usually 0.05 mol/! ! ~0.8 mol/I!
It is preferable to use dihydroxybenzenes and 1-phenyl-3-birapritones or p
When using a combination of -aminophenols, the former is 0.05 mol/l to 0.5 mol/l.

The latter at 0.06 mol/I! Preferably used with the following bonds:

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. Sulfite is used at least 0.25 mol/1, especially at least 0.3 mol/1, but if too large a quantity is added, it will precipitate in the developer and cause solution contamination, so the upper limit is 1.2 mol/1! It is desirable to do so.

As the alkaline agent used for setting the pH, ordinary water-soluble inorganic alkali metal salts (eg, sodium hydroxide, sodium carbonate, etc.) can be used.

In the developing solution used in the present invention, a buffering agent is added.
Boric acid described in No. 1-28708, JP-A No. 60-9343
The saccharides (e.g. sucrose), oximes (
e.g. acetoxime), phenol ti (e.g. 5-
sulfosalicylic acid), tertiary phosphates (eg, sodium salt, potassium salt), etc., and preferably boric acid is used.

For development lα (preferably lXl0-H ~ 3 x 10
- 0.1 mol/l or more, especially 0.2 mol/l-1 mol/l! of a moderating fJj agent (having a constant of 1 for the acid lysis of ``) can be added. By adding these compounds, Regardless of the silver color or blackening rate of the photosensitive material to be developed, it becomes possible to stably obtain the effects of ultra-high contrast and increased sensitivity due to hydrazines even when using an automatic processor.
The acid dissociation constant here means that the first, second, third, etc. are all compounds in the range 1X10-'' to 3X10-''.

Additives used in addition to the above components include pH adjusters such as potassium hydroxide and sodium carbonate; development inhibitors such as sodium bromide and potassium bromide; and ethylene glycol, diethylene glycol, triethylene glycol, and dimethylformamide. Organic solvents; alkanolamines such as jetanolamine and triethanolamine; development accelerators such as imidazole or its derivatives; mercapto compounds such as l-phenyl-5-mercaptotetrazole; indazole compounds such as 5-nitroindazole; Penztriazole compounds such as methylbenztriazole are used as antifoggants or black
peρper), and may also contain a toning agent, a surfactant, an antifoaming agent, a water softener, a hardening agent, etc. as required.

The fixing agent contains a diosulfate salt such as sodium thiosulfate or ammonium thiosulfate as an essential component, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed.The amount of the fixing agent used can be changed as appropriate, and is generally about 0.1～
Approximately 5 mol/I! It is.

Examples of acidic hardeners in the fixing solution in the present invention include water-soluble aluminum salts, chromium salts, and ethylenediaminetetraacetic acid complexes using trivalent iron compounds as oxidizing agents. Preferred compounds are water-soluble aluminum salts, such as aluminum chloride, aluminum sulfate, and potassium alum.

The amount added is preferably 0.02 mol to 0.2 mol/l, more preferably 0.03 to 0.08 mol/ρ.

As the nil dibasic acid, tartaric acid or a derivative thereof, citric acid or a derivative thereof can be used alone or in combination of two or more kinds. These compounds are used in fixer l! ! It is effective to contain 0.005 mol or more per liter, particularly 0.01 mol/f-0.03 mol/l.

Specifically, tartaric acid, potassium tartrate, sodium tartrate, potassium hydrogen tartrate, sodium hydrogen tartrate, potassium sodium tartrate, ammonium tartrate, ammonium potassium tartrate, aluminum potassium tartrate,
Potassium antimonyl tartrate, sodium antimonyl tartrate, lyticum hydrogen tartrate, lithium tartrate, magnesium hydrogen tartrate, potassium boron tartrate, lithium urium hexatrate, etc.

Examples of citric acid or its derivatives that are effective in the present invention include citric acid, sodium citrate, potassium citrate, lithium citrate, and ammonium citrate.

The fixing solution may optionally contain a preservative (e.g. sulfite, bisulfite) and a pH buffer (e.g. acetic acid, chloride).
, p[I regulator (e.g. sulfuric acid), Kill-1 agent (described above)
can include. Here, since the pH of the developer is high, the pH 111 additive is used in an amount of about 10 to 40 g/l, more preferably about 18 to 25 g/N.

The fixing temperature and time are the same as for developing, about 20'
C. to about 50.degree. C. for 10 seconds to 1 minute is preferred.

Next, the present invention will be explained with reference to examples.

In addition, the following formulation was used as a developer.

Treatment liquid formulation (11 Hydroquinone 50.0 gN
Methyl-p-aminophenol 0.3 g2 Sulfate Sodium hydroxide 18.0 g5
-Sulfosalicylic acid 55.0 g Potassium sulfite 110.0 g Ethylenediaminetetraacetic acid 1. Og potassium umide 5-methylbenzotriazole 2-mercaptobenzimidazole 5-sulfonic acid 3-(5-mercaptotetrazole) sodium benzenesulfonate N-n-butyljetanolamide 10.0 g 0.4 g 0. 3 g 15.0 Add sodium toluenesulfonate water to pH 11.6 Treatment liquid formulation (2) Hydroquinone 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone Potassium sulfite Disodium ethylenediaminetetraacetate 25. 0 90.0 g 2.0 g Potassium bromide 5.0 g 5-methylhensitriazole 0.2 g 2-mercaptobenzimidazole-5-sulfonic acid 0.3 g Sodium carbonate 50.0 g (add sodium hydroxide p II = I 0.6) Add water to prepare 1z emulsion A Add 7 g of gelatin and 4 g of KBr to water 11 and adjust the pH to 6
, 0, and while maintaining the solution temperature at 25°C, A g
NOs aqueous solution (AgNO: + 32.6 g) and KB
r aqueous solution (24.08 g of KBr) was added simultaneously over 4 minutes, then 25 g of gelatin was added and the pH was adjusted to 6.
5! : After adjusting and heating to 60'C and incubating at this temperature for 20 minutes, A g N Ox water soluble & (AgNOx
26 g) and KBr water-soluble 11 (KBrlB, 94 g)
were added simultaneously over 25 minutes. During this time, the silver potential of the solution was maintained at -20 mV.

After leaving it for 5 minutes, AgN0. Aqueous solution (A g
N0339 g) and a KBr aqueous solution (KBr comparative example gelatin water kept at 50°C) and ammonia in the presence of A g by a controlled double jet method.
NO3? A cubic monodisperse emulsion with an average grain size of 0.27 μm was prepared by adding the fI solution and the KBr solution simultaneously over a period of 60 minutes and maintaining the potential at +55 mV. After grain formation, the emulsion was washed with water and dispersed. (Emulsion a) '1-hydroxyethoxoethyl-3-(2-pyridyl)-5-(3(4-
Sulfobutyl)-5-chloropenzoxaprideneethylidene]-thiohydantoin potassium salt was added at 5X10-' mol per 1 mol of Ag, and other 4-hydroxy-6
-Methyl 1. 3. A dispersion of 3a7-titrazaindene, polyethyl acrylate, and 1,3-divinylsulfonyl-2-propanol as a hardening agent were added. Further, 8 .mu./n of hydrazine compound 1-15 of the present invention was added onto the polyethylene terephthalate film so that the amount of gel cloth I1 was 3.8 g/m, and a gelatin protective layer was coated thereon.

As a protective layer, gelatin, sodium dodecylbenzenesulfonate, F-based surfactant (CIIF+, 5C)z N (C3Hff)CH2C
A gelatin aqueous solution consisting of colloidal silica, a dispersion of polyethyl acrylate, a matting agent of polymethyl methacrylate, and a thickener of sodium polystyrene sulfonate was adjusted to have a gelatin coating amount of 1.6 g/m.

In order to examine the exposure latitude of the character manuscript of each sample,
After photographing a grade 7 Mincho font (Tsukasa) and Gothic font (Ren) phototypesetting manuscript with a Dainippon Screen camera (DSC351), it was developed with the developer formulation (1) at 34°C for 30 seconds. Fixed, washed with water, and dried. The photographing conditions were such that the fine lines in a certain area of the Mincho typeface were exposed to light at 40 μm, and the quality of the Gothic typeface (sharpness of the characters) was evaluated.

Evaluation is performed on a 6-level scale, with "6" representing the best quality and rlJ representing the worst quality. "6", "5", "4" are practical, "3" is a tug, but "2" is barely practical,
"l" is not practical.

The quality rating for the sample was 1.

Example 1 The compound l-15 in the emulsion layer of the sensitive material prepared in the comparative example was
The amount was increased to 0 mg/m, and the compound of the present invention ■
Sample B was prepared by adding -16 at a rate of 150 μ/d.

Sample B was prepared as shown in Sample 0 to Table 1 in which only the crystal habit and grain size of silver halide were changed at a control potential of 1 degree.

In order to examine the exposure latitude in the same manner as Comparative Example 1,
Photographs were taken, developed with developer formulation (2) at 38° C. for 30 seconds, fixed, washed with water, dried, and evaluated in the same manner.

In addition, sensitometry was performed to measure G.

Tomina crystal polishing potential a Cube Ma-V C Dodecahedron +lomV d)\al(To -20111V Cube 1v " Dodecahedron +]~V g A■i# -20mV h Cube +55mV Dodecahedron F1~V 3 5~4 ■6.O 17,2 17,8 16,5 I7.8 18.5 15, O 16,5 16,8 Notes Comparative example Invention 11 Good image quality can be obtained by using a +1-16 compound and processing with a pH 10.7 developer, but even better image quality can be obtained if the crystal habit is octahedral or tetradecahedral, regardless of the particle size. Can be done.

Example 2 Instead of hydrazine compound l-15 of sample B, ■-18
, ■-19, l-41, ■-45 each at 21) g/n (
, and 100 + ng/l-30 and l-38 each
L, M, N, O, and P were prepared as samples, photographed and developed in the same manner as in Example 1, and evaluated. Sensitometry was also performed to measure G.

Also, in the sample, only the raw materials L, M, N, O, and P were replaced with C and d, and ', I, 'M', N', O', P'
and prepare ', L'M'', N'', O', P'' on the sample,
In the same manner as in Example 1, images were photographed, developed, and evaluated.

Nucleating agent of the present invention (General 2N) and nucleation accelerator (-Tsuzuriyo combination of tetradecahedral particles Sede, It can be seen that good image quality can be obtained.

Claims (1)

[Scope of Claims] 1) A negative photosensitive material having at least one silver halide emulsion layer on a support, and having a hydrazine derivative of general formula (I) in the emulsion layer or other hydrophilic colloid layer. is processed with a developer having a pH of 11.2 or lower to form a high-contrast black-and-white image of @G@8 or higher, characterized in that the silver halide grains are octahedral or dodecahedral grains. Image forming method. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents an aliphatic group or an aromatic group, and R_
2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group, or an oxycarnebonyl group; G_1 is a carbonyl group;
It represents a sulfonyl group, a sulfoxy group, a ▲mathematical formula, a chemical formula, a table, etc.▼ group, or an iminomethylene group, and A_1 and A_2 are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or Represents a substituted or unsubstituted arylsulfonyl group or a substituted or unsubstituted acyl group. 2) The image forming method according to claim 1, wherein the silver halide emulsion layer or other hydrophilic colloid layer contains a compound represented by the following general formula (II). General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, Y represents a group that adsorbs to silver halide, and A represents a divalent linking group, B represents an amino group, an ammonium group, and a nitrogen-containing heterocycle, and the amino group may be substituted. m represents 1, 2 or 3, n
represents 0 or 1. )